Acylacetonitriles, process for preparation thereof and miticides containing the same

ABSTRACT

The acylacetonitrile compound of the invention is represented by the formula (1): 
                 
 
wherein R 1  represents —C(O)ZR 2 ; R 2  represents C 1-6  alkyl, C 1-4  haloalkyl or the like; Z represents oxygen or sulfur; X and Y independently represent halogen, C 1-6  alkyl or C 1-4  haloalkyl; and m and n are independently an integer of 1 to 3. The acylacetonitrile compound of the invention exhibits excellent miticidal and ovicidal activities for mites over a long period. Therefore, the acylacetonitrile compound of the invention is useful as a miticide.

This application is the U.S. National Phase under 35 U.S.C. §371 ofInternational Application PCT/JP01/06851, filed Aug. 9, 2001, whichclaims priority to Japanese Patent Application Nos. 2000-244738, filedAug. 11, 2000, and 2000-379844, filed Dec. 14, 2000. The InternationalApplication was published under PCT Article 21(2) in a language otherthan English.

TECHNICAL FIELD

The present invention relates to a novel acylacetonitrile compound, aprocess for preparing the compound, and a miticide containing thecompound.

BACKGROUND OF THE INVENTION

Japanese Unexamined Patent Publication No. 158137/1999 discloses acompound represented by the formula (A):

wherein R⁴ and R⁵ represent halogen, substituted or unsubstituted alkyl,or substituted or unsubstituted alkenyl; Y′ represents ═C(R⁶)— or ═N—;R⁶ represents hydrogen, halogen, alkyl or haloalkyl; m′ is an integer of0 to 5; and n′ is an integer of 1 to 4. The compound represented by theformula (A) is a compound exhibiting keto-enol tautomerism asillustrated in the following formula.

Said publication also discloses that the compounds represented by theformula (A) are useful as intermediates for preparing the acrylonitrilecompounds represented by the formula (B):

wherein R⁷ represents alkyl, haloalkyl or the like; and R⁴, R⁵, m′ andn′ are as defined above.

Further, said publication discloses that the compounds represented bythe formulas (A) and (B) exhibit miticidal activities.

However, said publication merely teaches in the examples that thecompounds represented by the formula (A) exhibit miticidal and ovicidalactivities for two-spotted spider mites when used at a highconcentration of 800 ppm.

The present inventors have confirmed through experiments that thecompounds represented by the formula (A) exhibit little miticidal andovicidal activities for two-spotted spider mites when used at a lowconcentration.

In addition, although said publication discloses that the acrylonitrilecompounds represented by the formula (B) are effective for mite control,the miticidal activities thereof are not satisfactory. Thus, inconsideration of the life cycle of mites, the demand exists for amiticide that can control the damage caused by mites over a long periodof about 14 to about 40 days depending on factors such as the kind ofmite, the type of plants to which the miticide will be applied, etc.However, the acrylonitrile compounds represented by the formula (B) arenot effective for controlling the damage caused by mites over a longperiod of about 14 to about 40 days.

Recently, some mites have developed resistance to the miticides thathave been in use for many years, making it difficult to control themwith conventional miticides. Thus, there are demands for the developmentof a novel miticide that can give excellent mite control.

DISCLOSURE OF THE INVENTION

It is an object of the present invention to provide an acylacetonitrilecompound that demonstrates excellent mite control even when the compoundis used at a low concentration.

It is another object of the invention to provide an acylacetonitrilecompound that can maintain excellent mite control over a long period.

It is a further object of the invention to provide an acylacetonitrilecompound that exhibits excellent mite control even for mites that havedeveloped resistance to conventional miticides.

It is also an object of the invention to provide a process for preparingthe acylacetonitrile compound described above.

It is still another object of the invention to provide a miticidecontaining the acylacetonitrile compound described above.

The present invention provides an acylacetonitrile compound representedby the formula (1):

wherein R¹ represents —C(O)ZR²; R² represents C₁₋₆ alkyl, C₁₋₄haloalkyl, C₂₋₄ alkenyl, C₂₋₄ alkynyl, C₁₋₆ alkoxy-C₁₋₄ alkyl, C₁₋₄alkylthio-C₁₋₄ alkyl or benzyl; Z represents oxygen or sulfur; X and Yindependently represent halogen, C₁₋₆ alkyl or C₁₋₄ haloalkyl; m and nare independently an integer of 1 to 3; and m X's and n Y's may be thesame or different, respectively.

The present invention provides a process for preparing theacylacetonitrile compound represented by the formula (1). The processcomprises reacting an α-substituted-phenylacetonitrile compoundrepresented by the formula (2):

wherein R¹, X and m are as defined above, with a benzoyl haliderepresented by the formula (3):

wherein Y and n are as defined above; and R³ represents halogen,to obtain the acylacetonitrile compound represented by the formula (1):

wherein R¹, X, m, Y and n are as defined above.

The present invention provides a miticide containing as an activeingredient the acylacetonitrile compound represented by the formula (1).

Acylacetonitrile Compound

In the present specification, the groups represented by each of R², X,Y, Z, and R³ can be exemplified as follows.

Examples of halogen atoms are fluorine, chlorine, bromine, iodine andthe like.

Examples of C₁₋₆ alkyl groups include C₁₋₆ linear or branched alkylgroups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl,sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, isohexyland the like.

Examples of C₁₋₄ haloalkyl groups are C₁₋₄ linear or branched alkylgroups substituted with 1 to 9, preferably 1 to 5, halogen atoms andinclude fluoromethyl, chloromethyl, bromomethyl, iodomethyl,difluoromethyl, trifluoromethyl, 1-fluoroethyl, 2-fluoroethyl,2-chloroethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, 1-fluoropropyl,2-chloropropyl, 3-fluoropropyl, 3-chloropropyl, 1-fluorobutyl,1-chlorobutyl, 4-fluorobutyl and the like.

Examples of C₂₋₄ alkenyl groups include C₂₋₄ linear or branched alkenylgroups such as vinyl, 1-propenyl, allyl, isopropenyl, 1-butenyl,2-butenyl, 3-butenyl, 1-methyl-2-propenyl, 1,3-butadienyl and the like.

Examples of C₂₋₄ alkynyl groups include C₂₋₄ linear or branched alkynylgroups such as ethynyl, 1-propynyl, 2-propynyl, 1-methyl-2-propynyl,1-butynyl, 2-butynyl, 3-butynyl and the like.

Examples of C₁₋₆ alkoxy groups are C₁₋₆ linear or branched alkoxy groupsand include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy,sec-butoxy, tert-butoxy, n-pentyloxy, isopentyloxy, neopentyloxy,n-hexyloxy, isohexyloxy and the like.

Examples of C₁₋₄ alkyl groups include C₁₋₄ linear or branched alkylgroups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl,sec-butyl and the like.

Examples of C₁₋₆ alkoxy-C₁₋₄ alkyl groups are C₁₋₄ linear or branchedalkyl groups substituted with 1 to 4, preferably 1 to 2, C₁₋₆ linear orbranched alkoxy groups and include methoxymethyl, ethoxymethyl,n-propoxymethyl, isopropoxymethyl, n-butoxymethyl, isobutoxymethyl,sec-butoxymethyl, tert-butoxymethyl, n-pentyloxymethyl,n-hexyloxymethyl, methoxyethyl, ethoxyethyl, n-propoxyethyl,isopropoxyethyl, n-butoxyethyl, isobutoxyethyl, sec-butoxyethyl,tert-butoxyethyl, 3-methoxypropyl, 3-ethoxypropyl, 3-ethoxybutyl and thelike.

Examples of C₁₋₄ alkylthio groups include C₁₋₄ linear or branchedalkylthio groups such as methylthio, ethylthio, n-propylthio,isopropylthio, n-butylthio, isobutylthio, sec-butylthio, tert-butylthioand the like.

Examples of C₁₋₄ alkylthio-C₁₋₄ alkyl groups are C₁₋₄ linear or branchedalkyl groups substituted with 1 to 4, preferably 1 to 2, C₁₋₄ linear orbranched alkylthio groups and include methylthiomethyl, methylthioethyl,ethylthiomethyl, ethylthioethyl, ethylthiopropyl, ethylthiobutyl,n-propylthiomethyl, isopropylthiomethyl, n-butylthioethyl and the like.

In acylacetonitrile compounds represented by the formula (1), Z ispreferably oxygen.

In acylacetonitrile compounds represented by the formula (1), X ispreferably halogen or C₁₋₆ alkyl.

In acylacetonitrile compounds represented by the formula (1), Y ispreferably one species selected from halogens and C₁₋₄ haloalkyls.

Among the acylacetonitrile compounds represented by the formula (1), thepreferred compounds are those wherein Z is oxygen, X is halogen or C₁₋₆alkyl, and Y is halogen and/or C₁₋₄ haloalkyl.

Among the acylacetonitrile compounds represented by the formula (1), themore preferred compounds are those wherein Z is oxygen, X is C₁₋₆ alkyl,and Y is C₁₋₄ haloalkyl.

Moreover, preferred acylacetonitrile compounds are those wherein thehalogen represented by X is chlorine, and the C₁₋₆ alkyl is isopropyl ortert-butyl; and those wherein m is 1. Most preferred compounds are thosewherein the phenyl ring is substituted with X at 4-position.

Also preferred are those acylacetonitrile compounds wherein C₁₋₄haloalkyl represented by Y is trihalogenomethyl, more preferablytrifluoromethyl; and those acylacetonitrile compounds wherein n is 1.Most preferred compounds are those wherein the phenyl ring issubstituted with Y at 2-position.

Method for Preparing Acylacetonitrile Compound

The acylacetonitrile compound of the present invention can be readilyprepared according to following reaction scheme 1.Reaction Scheme 1;

wherein R¹, X, Y, m, n, and R³ are as defined above.

As illustrated in the reaction scheme 1 above, the acylacetonitrilecompound of the invention represented by the formula (1) is prepared byreacting the α-substituted-phenylacetonitrile compound represented bythe formula (2) with the benzoyl halide represented by the formula (3).

The proportion of the α-substituted-phenylacetonitrile compound of theformula (2) to the benzoyl halide of the formula (3) used in thereaction is not limited and is suitably selected from a wide range. Thelatter is usually used in an amount of about 1 to about 5 moles,preferably about 1 mole, per mole of the former.

The above reaction can be carried out either in a suitable solvent or inthe absence of solvent. Usable solvents for the reaction are not limitedinsofar as they are inert to the reaction. Examples of solvents arehexane, cyclohexane, heptane and like aliphatic or alicyclichydrocarbons; benzene, chlorobenzene, toluene, xylene and like aromatichydrocarbons; methylene chloride, 1,2-dichloroethane, chloroform, carbontetrachloride and like halogenated hydrocarbons; diethyl ether,tetrahydrofuran, 1,4-dioxane and like ethers; methyl acetate, ethylacetate and like esters; acetone, methylethylketone and like ketones;N,N-dimethylformamide and like amides; dimethylsulfoxide and likesulfoxides; etc.

These solvents can be used alone or in combination of two or morespecies as required.

The reaction temperature of the above reaction, although not limited, isusually in the range of −20° C. to the boiling point of the solventused, preferably 0° C. to 25° C. The reaction time is usually in therange of about 0.5 to about 24 hours depending on factors such as thereaction temperature, etc.

The above reaction is preferably carried out in the presence of a base.A wide variety of known bases can be used. Examples are metallic sodium,metallic potassium and like alkali metals; sodium carbonate, potassiumcarbonate, sodium bicarbonate and like alkali metal carbonates; sodiumhydroxide, potassium hydroxide and like alkali metal hydroxides; sodiumhydride, potassium hydride and like alkali metal hydrides; sodiummethoxide, sodium ethoxide, potassium tert-butoxide and like alkalimetal alkoxides; and triethylamine, pyridine and like organic bases.

These bases can be used alone or in combination of two or more species.

The amount of the base is equivalent or more, preferably about 1 toabout 5 equivalents, relative to the α-substituted-phenylacetonitrilecompound of the formula (2).

When an organic base such as triethylamine, pyridine or the like isused, it can be used in large excess to serve also as a reactionsolvent.

The α-substituted-phenylacetonitrile compounds represented by theformula (2) used as starting compound in reaction scheme 1 include novelcompounds as well as known compounds, and are prepared according to, forexample, the following reaction scheme 2.Reaction Scheme 2;

wherein R¹, X and m are as defined above; M represents halogen or —ZR²;and R² and Z are as defined above.

As illustrated in the reaction scheme 2 above, theα-substituted-phenylacetonitrile compound represented by the formula (2)is prepared in a simple manner by reacting the phenylacetonitrilerepresented by the formula (4) with the compound represented by theformula (5).

The proportion of the phenylacetonitrile represented by the formula (4)to the compound represented by the formula (5) used in the reaction isnot limited and is suitably selected from a wide range. The latter isusually used in an amount of about 1 to about 10 moles, preferably about1 mole, per mole of the former.

The above reaction can be carried out in a suitable solvent or in theabsence of solvent. Usable solvents for the reaction are not limitedinsofar as they are inert to the reaction. Examples of solvents arehexane, cyclohexane, heptane and like aliphatic or alicyclichydrocarbons; benzene, chlorobenzene, toluene, xylene and like aromatichydrocarbons; methylene chloride, 1,2-dichloroethane, chloroform, carbontetrachloride and like halogenated hydrocarbons; diethyl ether,tetrahydrofuran, 1,4-dioxane and like ethers; methyl acetate, ethylacetate and like esters; acetone, methylethylketone and like ketones;N,N-dimethylformamide and like amides; dimethylsulfoxide and likesulfoxides; etc.

These solvents can be used alone or in combination of two or morespecies as required.

The reaction temperature of the above reaction, although not limited, isin the range of −20° C. to the boiling point of the solvent used,preferably 0° C. to 25° C. Usually, the reaction is completed in about0.5 to about 24 hours depending on factors such as the reactiontemperature, etc.

The above reaction is preferably carried out in the presence of a base.A wide variety of known bases can be used. Examples are metallic sodium,metallic potassium and like alkali metals; sodium carbonate, potassiumcarbonate, sodium bicarbonate and like alkali metal carbonates; sodiumhydroxide, potassium hydroxide and like alkali metal hydroxides; sodiumhydride, potassium hydride and like alkali metal hydrides; sodiummethoxide, sodium ethoxide, potassium tert-butoxide and like alkalimetal alkoxides; and triethylamine, pyridine and like organic bases.

These bases can be used alone or in combination of two or more species.

The amount of base is usually equivalent or more, preferably about 1 toabout 5 equivalents, relative to the phenylacetonitrile of the formula(4).

An organic base such as triethylamine, pyridine or the like can be usedin large excess to serve also as a reaction solvent.

Among the α-substituted-phenylacetonitrile compounds represented by theformula (2) as prepared above, those α-substituted-phenylacetonitrilecompounds represented by the following formula (2a) and having atert-butyl substituent at 4-position of the phenyl ring are novelcompounds, which are not described in the literature:

wherein R¹ is as defined above.

The benzoyl halides represented by the formula (3) and used as startingcompound in reaction scheme 1 are either known compounds or compoundsthat can be easily prepared according to the known methods described in,for example, Org. Synth., IV, 715 (1963), etc.

The phenylacetonitriles represented by the formula (4) and the compoundsrepresented by the formula (5) used as starting compounds in reactionscheme 2 are, respectively, either known compounds or the compounds thatcan be easily prepared according to the known methods described in, forexample, Org. Synth., I, 107 (1941), Ann., 35 283. (1840), etc.

The acylacetonitrile compounds represented by the formula (1) preparedaccording to the method illustrated in reaction scheme 1 and theα-substituted-phenylacetonitriles represented by the formula (2)prepared according to the method illustrated in reaction scheme 2 can beeasily isolated from the respective reaction mixtures and purified by aknown isolating and purifying procedure such as filtration, solventextraction, distillation, recrystallization, column chromatography, etc.

Miticide

The compound of the present invention can be used as a miticide byitself. However, it is preferable to use in combination with a solidcarrier, liquid carrier or gaseous carrier (propellant), and optionallywith a surfactant and other adjuvants added thereto; it is formulatedinto various forms such as oil solutions, emulsifiable concentrates,wettable powders, flowables, granules, dusts, aerosols, fumigants or thelike according to known preparation methods.

The acylacetonitrile compound of the invention is generally contained inthese formulations in a proportion of 0.01 to 95 wt. %, preferably 0.1to 50 wt. %.

Examples of solid carriers usable for a component in the formulationsinclude those solid carriers used in known miticides such as clays,inorganic minerals, chemical fertilizers, etc. Specific examples ofclays are kaolin clay, diatomaceous earth, water-containing syntheticprecipitated silica, bentonite, fubasami clay, acid clay and the like.Specific examples of inorganic minerals are talc, ceramic, celite,quartz, sulfur, active carbon, calcium carbonate, hydrated silica andthe like. Specific examples of chemical fertilizers are ammoniumsulfate, ammonium phosphate, ammonium nitrate, urea, ammonium chlorideand the like. These solid carriers are used in a fine, powdery orgranular form.

Examples of liquid carriers usable for the preparation of formulationsinclude those known liquid carriers used in miticides such as water,alcohols, ketones, aromatic hydrocarbons, aliphatic hydrocarbons,esters, nitrites, ethers, acid amides, halogenated hydrocarbons,dimethyl sulfoxide, vegetable oils, etc. Specific examples of alcoholsare methanol, ethanol and the like. Specific examples of ketones areacetone, methylethylketone and the like. Specific examples of aromatichydrocarbons are benzene, toluene, xylene, ethylbenzene,methylnaphthalene and the like. Specific examples of aliphatichydrocarbons are hexane, cyclohexane, kerosene, light oil and the like.Specific examples of esters are ethyl acetate, butyl acetate and thelike. Specific examples of nitrites are acetonitrile, isobutyronitrileand the like. Specific examples of ethers are diisopropyl ether, dioxaneand the like. Specific examples of acid amides areN,N-dimethylformamide, N,N-dimethylacetamide and the like. Specificexamples of halogenated hydrocarbons are dichloromethane,trichloroethane, carbon tetrachloride and the like. Specific examples ofvegetable oils are soybean oil, cottonseed oil and the like.

Examples of gaseous carriers usable for the preparation of formulationsinclude those known gaseous carriers used in miticides such as butanegas, LPG (liquefied petroleum gas), dimethyl ether, carbon dioxide gasand the like.

As a surfactant, known surfactants can be widely used. Examples includealkyl sulfates, alkylsulfonates, alkylarylsulfonates, alkyl aryl ethersand polyoxyethylene adducts thereof, polyethylene glycol ethers,polyhydric alcohol esters, sugar alcohol compounds and the like.

Examples of adjuvants include fixing agents, dispersants, stabilizers,etc.

Examples of the fixing agents and dispersants include casein, gelatin,polysaccharides, lignin derivatives, bentonite, sugars, water-solublesynthetic polymers and the like. Specific examples of polysaccharidesinclude starch, gum arabic, cellulose derivatives, alginic acid and thelike. Specific examples of synthetic water-soluble polymers includepolyvinyl alcohol, polyvinyl pyrrolidone, polyacrylic acids and thelike.

Stabilizers to be used include a wide range of known stabilizers usuallyused in this field. Examples are PAP (acidic isopropyl phosphate), BHT(2,6-di-tert-butyl-4-methylphenol), BHA (mixture of2-tert-butyl-4-methoxyphenol and 3-tert-butyl-4-methoxyphenol),vegetable oils (e.g., epoxidized linseed oil, etc.), mineral oils, fattyacids or esters thereof, etc.

The miticide of the invention can be used as it is or as diluted, forexample, with water. The miticide can also be used in a mixture withother insecticides, nematocides, acaricides, fungicides, herbicides,plant growth control agents, synergists, soil conditioners, animal feedsand the like; and can be simultaneously used with such agents withoutmixing.

As a miticide for agricultural use, the compound of the invention isusually applied in an amount of 0.1 to 500 g, preferably 1 to 100 g, per1,000 m of the area. When the compound of the invention is used in theform of emulsifiable concentrates, wettable powders, flowables or thelike and diluted with water, the compound is usually applied in aconcentration of 1 to 1,000 ppm, preferably 10 to 500 ppm. When themiticide of the invention is used in the form of granules, powders orthe like, it can be applied as such without dilution.

The amount or concentration of application, although exemplified above,can be suitably increased or decreased according to the type offormulation, time of application, place of application, method ofapplication, kind of insect, severity of damage, etc.

The mites against which the miticide of the invention is effective areplant parasites, for example, two-spotted spider mites, carmine spidermites, citrus red mites, Kanzawa spider mites, fruit tree red spidermites (European red mites), broad mites, pink citrus rust mites, bulbmites and the like.

EFFECT OF THE INVENTION

The acylacetonitrile compounds of the invention represented by theformula (1) are effective, even at a low dose, against harmful mites andthe like.

The acylacetonitrile compounds of the invention exhibit excellent mitecontrol against various mites even when used at a low concentration. Theterm “mite control” employed herein means miticidal activities effectiveat every stage of the life cycle of mites (e.g., egg, larva and imago).

The acylacetonitrile compounds of the invention exhibit excellent mitecontrol over an extended period of 14 to 40 days.

The acylacetonitrile compounds of the invention show excellent mitecontrol even for those mites having developed resistance to conventionalmiticides.

The acylacetonitrile compounds of the invention are satisfactory withregard to safety in that they do not affect plants; honeybee,Trichogramma evanescens, Encarsia formosa, minute pirate bug (Oriusspp.) and like beneficial insects; Phytoseiulus persimilis and likebeneficial predacious mites; etc.

BEST MODE FOR CARRYING OUT THE INVENTION

The present invention is described in more detail with reference to thefollowing preparation examples, formulation examples and test examples,but the scope of the present invention is not limited by these examples.

PREPARATION EXAMPLE 1

Preparation of Methyl 2-(4-Tert-Butylphenyl)Cyanoacetate (Compound No.(2)-1)

0.66 g (16.5 mmols) of sodium hydride and 2.6 g (15.0 mmols) of4-tert-butylphenylacetonitrile were suspended in 50 ml oftetrahydrofuran. To the suspension was added dropwise 1.95 g (16.5mmols) of dimethyl carbonate dissolved in 10 ml of tetrahydrofuran whilestirring at room temperature. The mixture was refluxed with heating for2 hours, and the solvent was distilled off under reduced pressure. Waterwas added to the residue, and the residue was acidified by dilutedhydrochloric acid and twice extracted with 30 ml of ethyl acetate. Theethyl acetate extraction solutions were mixed, washed with a saturatedbrine solution, and dried over anhydrous magnesium sulfate. The solventwas distilled off under reduced pressure. The residue thus-obtained waspurified by silica gel column chromatography (n-hexane:ethylacetate=2:1), giving 1.8 g of the desired product (yield 52%)

α-Substituted-phenylacetonitrile compounds represented by the formula(2) were prepared in the same manner as described in preparation example1 except that the 4-tert-butyl phenylacetonitrile was replaced withcorresponding phenylacetonitriles.

Table 1 shows the compounds thus obtained and their properties, andtable 2 shows the ¹H-NMR data of the compounds.

TABLE 1

Compound No. (2)-No. R¹ Property  1 —CO₂CH₃ Viscous oil   2 —CO₂CH₂CH₃Viscous oil   3 —CO₂CH(CH₃)₂ Viscous oil   4 —CO₂C(CH₃)₃ Viscous oil   5—CO₂CH₂(CH₂)₄CH₃ Viscous oil   6 —CO₂CH₂C₆H₅ Viscous oil   7—CO₂CH₂CH═CH₂ Viscous oil   8 —CO₂CH₂C≡CH Viscous oil   9 —CO₂CH₂CF₃Viscous oil 10 —CO₂CH₂CH₂OCH₃ Viscous oil 11 —CO₂CH₂CH₂OC₂H₅ Viscous oil12 —CO₂CH₂CH₂OCH₂CH₂CH₃ Viscous oil 13 —CO₂CH₂CH₂OCH (CH₃)₂ Viscous oil14 —CO₂CH₂CH₂OCH₂(CH₂)₂CH₃ Viscous oil 15 —CO₂CH₂CH₂OC(CH₃)₃ Viscous oil16 —CO₂CH₂CH₂SCH₃ Viscous oil 17 —C(O)SCH₃ Viscous oil 18 —C(O)SC₂H₅Viscous oil 19 —C(O)SCH₂CH₂CH₃ Viscous oil 20 —C(O)SCH(CH₃)₂ Viscous oil21 —C(O)SCH₂(CH₂)₂CH₃ Viscous oil 22 —C(O)SCH₂(CH₂)₄CH₃ Viscous oil

TABLE 2

Compound No. (2)-No. ¹H-NMR (CDCl₃, ppm)  1 1.32(s, 9H), 3.81(s, 3H),4.71(s, 1H), 7.41(dd, 4H)  2 1.2-1.4(m, 12H), 4.25(q, 2H), 4.69(s, 1H),7.41(dd, 4H)  3 1.2-1.4(m, 15H), 4.65(s, 1H), 5.0-5.1(m, 1H), 7.40(dd,4H)  4 1.32(s, 9H), 1.46(s, 9H), 4.58(s, 1H), 7.35(d, 2H), 7.40(d, 2H) 5 0.8-0.9(m, 3H), 1.2-1.4(m, 15H), 1.6-1.7(m, 2H), 4.18(t, 2H), 4.69(s,1H), 7.40(dd, 4H)  6 1.32(s, 9H), 4.73(s, 1H), 5.20(s, 2H), 7.2-7.5(m,9H)  7 1.31(s, 9H), 4.67(dm, 2H), 4.73(s, 1H), 5.26(dd, 1H), 5.31(dd,1H), 5.8-6.0 (m, 1H), 7.38(d, 2H), 7.44(d, 2H)  8 1.32(s, 9H), 2.52(t,1H), 4.75(s, 1H), 4.76(dd, 2H), 7.38(d, 2H), 7.44(d, 2H)  9 1.32(s, 9H),4.5-4.6(m, 2H), 4.81(s, 1H), 7.38(d, 2H), 7.45(d, 2H) 10 1.32(s, 9H),3.09(s, 3H), 3.6-3.65(m, 2H), 4.3-4.35(m, 2H), 4.75(s, 1H), 7.40(d, 2H),7.41(d, 2H) 11 1.32(s, 9H), 1.15(t, 3H), 3.45(q, 2H), 3.7-3.75(m, 2H),4.3-4.35(m, 2H), 4.74(s, 1H), 7.38(d, 2H), 7.40(d, 2H) 12 0.88(t, 3H),1.33(s, 9H), 1.5-1.6(m, 2H), 3.36(t, 2H), 3.6-3.36(m, 2H), 4.3-4.35(m,2H), 4.74(s, 1H), 7.38(d, 2H), 7.43(d, 2H) 13 1.08(d, 3H), 1.10(d, 3H),1.31(s, 9H), 3.5-3.6(m, 1H), 3.6-3.65(m, 2H), 4.3-4.35(m, 2H), 4.74(s,1H), 7.41(s, 4H) 14 0.91(t, 3H), 1.32(s, 9H), 1.3-1.4(m, 2H), 1.5-1.6(m,2H), 3.40(t, 2H), 3.6- 3.65(m, 2H), 4.3-4.35(m, 2H), 4.74(s, 1H),7.38(d, 2H), 7.43(d, 2H) 15 1.12(s, 9H), 1.31(s, 9H), 3.5-3.55(m, 2H),4.3-4.35(m, 2H), 4.73(s, 1H), 7.41(s, 4H) 16 1.32(s, 9H), 2.11(s, 3H),2.73(t, 2H), 4.35(t, 2H), 4.73(s, 1H), 7.38(d, 2H), 7.44(d, 2H) 171.32(s, 9H), 2.44(s, 3H), 4.79(s, 1H), 7.46(d, 2H), 7.50(d, 2H) 181.26(t, 3H), 1.32(s, 9H), 2.91(q, 2H), 4.77(s, 1H), 7.38(d, 2H), 7.44(d,2H) 19 0.95(t, 3H), 1.32(s, 9H), 1.5-1.7(m, 2H), 2.90(dt, 2H), 4.78(s,1H), 7.37(d, 2H), 7.43(d, 2H) 20 1.3-1.4(m, 15H), 3.6-3.7(m, 1H),4.73(s, 1H), 7.35(d, 2H), 7.43(d, 2H) 21 0.89(t, 3H), 1.3-1.4(m, 2H),1.33(s, 9H), 1.5-1.6(m, 2H), 2.91(t, 2H), 4.77 (s, 1H), 7.36(d, 2H),7.43(d, 2H) 22 0.85(t, 3H), 1.32(s, 9H), 1.2-1.4(m, 6H), 1.5-1.6(m, 2H),2.91(t, 2H), 4.77 (s, 1H), 7.36(d, 2H), 7.43(d, 2H)

PREPARATION EXAMPLE 2

Preparation of Methyl2-(4-Chlorophenyl)-2-(2-Trifluoromethylbenzoyl)Cyanoacetate (CompoundNo. 30)

0.10 g (2.6 mmols) of sodium hydride was suspended in 20 ml oftetrahydrofuran. To the suspension was added dropwise, while stirringand cooling, 5 ml of a tetrahydrofuran solution in which 0.42 g (2.0mmols) of methyl 2-(4-chlorophenyl)cyanoacetate and 0.41 g (2.6 mmols)of 2-trifluoromethylbenzoyl chloride had been dissolved. The mixture wasstirred at room temperature over night. The reaction mixture was pouredinto ice water. The water phase thereof was acidified by dilutedhydrochloric acid and twice extracted with 30 ml of ethyl acetate. Theethyl acetate extraction solutions were mixed, washed with a saturatedbrine solution, and dried over anhydrous magnesium sulfate. The solventwas distilled off under reduced pressure. The residue thus-obtained waspurified by silica gel column chromatography (n-hexane:benzene=1:1),giving 0.45 g of the desired product (yield 59%).

Acylacetonitrile compounds represented by the formula (1) of theinvention were prepared in the same manner as described in preparationexample 2 except that the methyl 2-(4-chlorophenyl)cyanoacetate wasreplaced with corresponding α-substituted-phenylacetonitrile compounds,and/or the 2-trifluoromethylbenzoyl chloride was replaced withcorresponding benzoyl chlorides.

Table 3 shows the compounds thus obtained and their properties, andtable 4 shows the ¹H-NMR data of the compounds.

TABLE 3

Compound No. Xm Yn R¹ Melting point(° C.)  1 4-C(CH₃)₃ 2-CF₃ —CO₂CH₃137-139  2 4-C(CH₃)₃ 2-CF₃ —CO₂C₂H₅ 141-142  3 4-C(CH₃)₃ 2-CF₃—CO₂CH(CH₃)₂ 141-142  4 4-C(CH₃)₃ 2-CF₃ —CO₂C(CH₃)₃ 137-138  5 4-C(CH₃)₃2-CF₃ —CO₂CH₂(CH₂)₄CH₃ 83-84  6 4-C(CH₃)₃ 2-CF₃ —CO₂CH₂C₆H₅ Viscous oil 7 4-C(CH₃)₃ 2-CF₃ —CO₂CH₂CH═CH₂ 107-108  8 4-C(CH₃)₃ 2-CF₃ —CO₂CH₂C≡CH106-108  9 4-C(CH₃)₃ 2-CF₃ —CO₂CH₂CF₃ 94-95 10 4-C(CH₃)₃ 2-CF₃—CO₂CH₂CH₂OCH₃ 73-74 11 4-C(CH₃)₃ 2-CF₃ —CO₂CH₂CH₂OC₂H₅ Viscous oil 124-C(CH₃)₃ 2-CF₃ —CO₂CH₂CH₂OCH₂CH₂CH₃ Viscous oil 13 4-C(CH₃)₃ 2-CF₃—CO₂CH₂CH₂OCH(CH₃)₂ Viscous oil 14 4-C(CH₃)₃ 2-CF₃—CO₂CH₂CH₂OCH₂(CH₂)₂CH₃ Viscous oil 15 4-C(CH₃)₃ 2-CF₃—CO₂CH₂CH₂OC(CH₃)₃ Viscous oil 16 4-C(CH₃)₃ 2-CF₃ —CO₂CH₂CH₂SCH₃ Viscousoil 17 4-C(CH₃)₃ 2-CF₃ —C(O)SCH₃ 113-116 18 4-C(CH₃)₃ 2-CF₃ —C(O)SC₂H₅113-114 19 4-C(CH₃)₃ 2-CF₃ —C(O)SCH₂CH₂CH₃ 85-87 20 4-C(CH₃)₃ 2-CF₃—C(O)SCH(CH₃)₂ 81-84 21 4-C(CH₃)₃ 2-CF₃ —C(O)SCH₂(CH₂)₂CH₃ Viscous oil22 4-C(CH₃)₃ 2-CF₃ —C(O)SCH₂(CH₂)₄CH₃ Viscous oil 23 2-Cl 2-CF₃ —CO₂C₂H₅71-73 24 3-Cl 2-CF₃ —CO₂C₂H₅ 89-92 25 4-Cl 2-CF₃ —CO₂C₂H₅ Viscous oil 262,4-Cl₂ 2-CF₃ —CO₂C₂H₅ 70-72 27 2,6-Cl₂ 2-CF₃ —CO₂C₂H₅ 132-134 283,4-Cl₂ 2-CF₃ —CO₂C₂H₅ 66-68 29 3,5-Cl₂ 2-CF₃ —CO₂C₂H₅ 123-124 30 4-Cl2-CF₃ —CO₂CH₃ 89-92 31 4-Cl 2-CF₃ —CO₂CH₂CH₂CH₃ 60-62 32 4-Cl 2-CF₃—CO₂CH(CH₃)₂ Viscous oil 33 4-Cl 2-CF₃ —CO₂CH₂(CH₂)₂CH₃ 42-43 34 4-Cl2-CF₃ —CO₂C(CH₂)₃ 94-97 35 4-Cl 2-CF₃ —CO₂CH₂CH(CH₃)₂ 94-96 36 4-C(CH₃)₃2-CF₃, —CO₂C₂H₅ 111-112 4-F 37 4-C(CH₃)₃ 2-CF₃, —CO₂C₂H₅ 110-112 5-F 384-C(CH₃)₃ 2-CF₃, —CO₂C₂H₅ Viscous oil 6-F 39 4-Cl 2-Cl —CO₂C₂H₅ Viscousoil 40 4-Cl 2-F —CO₂CH₃ 59-60 41 4-Cl 2-Br —CO₂CH₃ Viscous oil 42 4-Cl2-CH₃ —CO₂CH₃ 65-68 43 4-Cl 2,6-F₂ —CO₂CH₃ Viscous oil 44 4-F 2-CF₃—CO₂C₂H₅ 75-76 45 4-Br 2-CF₃ —CO₂C₂H₅ 43-45 46 4-CH₃ 2-CF₃ —CO₂C₂H₅57-58 47 4-CF₃ 2-CF₃ —CO₂C₂H₅ Viscous oil 48 4-CH(CH₃)₂ 2-CF₃ —CO₂C₂H₅79-80 49 4-CH₂CH(CH₃)₂ 2-CF₃ —CO₂C₂H₅ 38-40

TABLE 4

Compound No. ¹H-NMR (CDCl₃, ppm)  1 1.35(s, 9H), 3.92(s, 3H), 7.07(d,1H), 7.4-7.7(m, 6H), 7.78(d, 1H)  2 1.34(t, 3H), 1.35(s, 9H), 4.2-4.5(m,2H), 7.07(d, 1H), 7.4-7.5(m, 3H), 7.5-7.6(m, 3H), 7.78(d, 1H)  31.2-1.4(m, 15H), 5.1-5.2(m, 1H), 7.08(d, 1H), 7.4-7.6(m, 6H), 7.79(d,1H)  4 1.35(s, 9H), 1.52(s, 9H), 7.05(d, 1H), 7.4-7.6(m, 6H), 7.77(d,1H)  5 0.8-1.0(m, 3H), 1.2-1.4(m, 15H), 1.6-1.8(m, 2H), 4.2-4.4(m, 2H),7.07(d, 1H), 7.4-7.6(m, 6H), 7.78(d, 1H)  6 1.34(s, 9H), 5.3-5.4(m, 2H),7.04(d, 1H), 7.3-7.6(m, 11H), 7.75(d, 1H)  7 1.35(s, 9H), 4.7-4.9(m,2H), 5.30(dd, 1H), 5.38(dd, 1H), 5.9-6.0(m, 1H), 7.07(d, 1H), 7.4-7.7(m, 6H), 7.78(d, 1H)  8 1.34(s 9H), 2.55(t, 1H), 4.87(d, 2H), 7.10(d,1H), 7.4-7.6(m, 6H), 7.77(d, 1H)  9 1.36(s, 9H), 4.6-4.8(m, 2H), 6.98(d,1H), 7.4-7.7(m, 6H), 7.80(d, 1H) 10 1.35(s, 9H), 3.36(s, 3H),3.6-3.65(m, 2H), 4.4-4.5(m, 2H), 7.14(d, 1H), 7.4-7.6(m, 6H), 7.78(d,1H) 11 1.17(t, 3H), 1.34(s, 9H), 3.50(q, 2H), 3.6-3.7(m, 2H), 4.4-4.5(m,2H), 7.15(d, 1H), 7.4-7.6(m, 6H), 7.80(d, 1H) 12 0.89(t, 3H), 1.34(s,9H), 1.5-1.6(m, 2H), 3.40(t, 2H), 3.65-3.7(m, 2H), 4.4-4.5(m, 2H),7.15(d, 1H), 7.4-7.6(m, 6H), 7.79(d, 1H) 13 1.1-1.2(m, 6H), 1.34(s, 9H),3.5-3.6(m, 1H), 3.6-3.65(m, 2H), 4.3-4.35(m, 2H), 7.14(d, 1H), 7.4-7.6(m, 6H), 7.77(d, 1H) 14 0.90(t, 3H), 1.34(s, 9H), 1.3-1.4(m, 2H),1.5-1.6(m, 2H), 3.44(t, 2H), 3.6-3.7(m, 2H), 4.4-4.5 (m, 2H), 7.15(d,1H), 7.4-7.6(m, 6H), 7.77(d, 1H) 15 1.16(s, 9H), 1.34(s, 9H),3.6-3.65(m, 2H), 4.4-4.45(m, 2H), 7.17(d, 1H), 7.4-7.6(m, 6H), 7.76(d,1H) 16 1.35(s, 9H), 2.14(s, 3H), 2.77(t, 2H), 4.4-4.6(m, 2H), 7.08(d,1H), 7.4-7.6(m, 6H), 7.77(d, 1H) 17 1.35(t, 3H), 2.42(s, 3H), 7.19(d,1H), 7.5-7.65(m, 6H), 7.77(d, 1H) 18 1.29(t, 3H), 1.35(s, 9H), 2.99(qd,2H), 7.21(d, 1H), 7.4-7.6(m, 6H), 7.76(d, 1H) 19 0.97(t, 3H), 1.35(s,9H), 1.5-1.7(m, 2H), 2.8-3.1(m, 2H), 7.22(d, 1H), 7.4-7.7(m, 6H),7.76(d, 1H) 20 1.2-1.4(m, 15H), 3.6-3.8(m, 1H), 7.23(d, 1H), 7.4-7.7(m,6H), 7.76(d, 1H) 21 0.91(t, 3H), 1.3-1.4(m, 2H), 1.35(s, 9H), 1.5-1.6(m,2H), 2.9-3.1(m, 2H), 7.22(d, 1H), 7.4-7.6 (m, 6H), 7.76(d, 1H) 220.87(t, 3H), 1.2-1.4(m, 6H), 1.35(s, 9H), 1.5-1.7(m, 2H), 2.9-3.1(m,2H), 7.22(d, 1H), 7.4-7.6 (m, 6H), 7.76(d, 1H) 23 1.28(t, 3H), 4.15(q,2H), 7.3-7.4(m, 2H), 7.4-7.5(m, 2H), 7.7-7.9(m, 3H), 8.2-8.3(m, 1H) 241.34(t, 3H), 4.3-4.5(m, 2H), 7.14(d, 1H), 7.4-7.7(m, 6H), 7.80(d, 1H) 251.34(t, 3H), 4.3-4.5(m, 2H), 7.12(d, 1H), 7.4-7.8(m, 6H), 7.79(d, 1H) 261.30(t, 3H), 4.18(q, 2H), 7.30(dd, 1H), 7.40(d, 1H), 7.49(d, 1H),7.7-7.8(m, 2H), 7.8-7.9(m, 1H), 8.2-8.3(m, 1H) 27 1.28(t, 3H), 4.19(q,2H), 7.28(d, 1H), 7.39(s, 1H), 7.42(d, 1H), 7.7-7.8(m, 2H), 7.8-7.9 (m,1H), 8.2-8.3(m, 1H) 28 1.34(t, 3H), 4.3-4.5(m, 2H), 7.19(d, 1H),7.5-7.9(m, 6H) 29 1.35(t, 3H), 4.3-4.5(m, 2H), 7.21(d, 1H), 7.50(d, 1H),7.5-7.7(m, 4H), 7.81(d, 1H) 30 3.93(s, 3H), 7.12(d, 1H), 7.4-7.5(m, 3H),7.6-7.7(m, 3H), 7.80(d, 1H) 31 0.96(t, 3H), 1.6-1.8(m, 2H), 4.2-4.4(m,2H), 7.11(d, 1H), 7.4-7.5(m, 3H), 7.6-7.7(m, 3H), 7.79(d, 1H) 32 1.28(d,3H), 1.34(d, 3H), 5.1-5.2(m, 2H), 7.13(d, 1H), 7.4-7.5(m, 3H),7.6-7.7(m, 3H), 7.89(d, 1H) 33 0.93(t, 3H), 1.3-1.5(m, 2H), 1.6-1.8(m,2H), 4.2-4.4(m, 2H), 7.10(d, 1H), 7.4-7.6(m, 3H), 7.6-7.7(m, 3H),7.62(d, 1H) 34 1.51(s, 9H), 7.13(d, 1H), 7.3-7.7(m, 6H), 7.79(d, 1H) 350.95(d, 6H), 1.9-2.1(m, 1H), 4.0-4.2(m, 2H), 7.10(d, 1H), 7.4-7.5(m,3H), 7.6-7.7(m, 3H), 7.62(d, 1H) 36 1.3-1.4(m, 12H), 4.2-4.5(m, 2H),7.1-7.2(m, 2H), 7.4-7.6(m, 5H) 37 1.3-1.4(m, 12H), 4.2-4.5(m, 2H),6.65(m, 1H), 7.2-7.3(m, 1H), 7.4-7.6(m, 4H), 7.7-7.8 (m, 1H) 381.3-1.4(m, 12H), 4.2-4.5(m, 2H), 7.3-7.4(m, 1H), 7.45(d, 1H), 7.5-7.7(m,4H) 39 1.33(t, 3H), 4.2-4.5(m, 2H), 7.1-7.2(m, 2H), 7.3-7.4(m, 4H),7.5-7.6(m, 2H) 40 3.91(s, 3H), 7.20(dd, 1H), 7.2-7.5(m, 5H), 7.6-7.7(m,1H), 7.8-7.9(m, 1H) 41 3.93(s, 3H), 7.17(d, 1H), 7.3-7.4(m, 2H),7.4-7.5(m, 2H), 7.6-7.7(m, 3H) 42 2.48(s, 3H), 3.91(s, 3H), 7.10(t, 1H),7.3-7.5(m, 6H), 7.56(dd, 1H) 43 3.93(s, 3H), 6.9-7.1(m, 2H), 7.4-7.6(m,5H) 44 1.34(t, 3H), 4.3-4.5(m, 2H), 7.10(d, 1H), 7.1-7.2(m, 2H), 7.50(t,1H), 7.6-7.8(m, 3H), 7.79(d, 1H) 45 1.34(t, 3H), 4.3-4.5(m, 2H), 7.12(d,1H), 7.5-7.7(m, 6H), 7.79(d, 1H) 46 1.34(t, 3H), 2.41(s, 3H), 4.3-4.5(m,2H), 7.04(d, 1H), 7.2-7.3(m, 2H), 7.45(t, 1H), 7.5- 7.6(m, 3H), 7.77(d,1H) 47 1.34(t, 3H), 4.3-4.5(m, 2H), 7.17(d, 1H), 7.53(t, 1H), 7.6-7.8(m,6H) 48 1.28(d, 6H), 1.34(t, 3H), 2.9-3.1(m, 1H), 4.2-4.5(m, 2H), 7.06(d,1H), 7.34(d, 2H), 7.46 (t, 1H), 7.5-7.7(m, 3H), 7.78(d, 1H) 49 0.91(d,6H), 1.34(t, 3H), 1.8-2.0(m, 1H), 2.52(d, 2H), 4.3-4.5(m, 2H), 7.02(d,1H), 7.26 (d, 2H), 7.43(t, 1H), 7.5-7.6 (m, 3H), 7.77(d, 1H)

Given below are formulation examples in which the parts refers to partsby weight.

FORMULATION EXAMPLE 1 (EMULSIFIABLE CONCENTRATE)

10 parts of each compound of the invention was dissolved in 45 parts ofSolvesso 150 and 35 parts of N-methylpyrrolidone. 10 parts of emulsifier(trade name: Sorpol 3005X, manufactured by Toho kagaku Co., Ltd.) wasadded thereto. These ingredients were mixed while stirring, therebyproducing a 10% emulsifiable concentrate.

FORMULATION EXAMPLE 2 (WETTABLE POWDER)

20 parts of each compound of the invention was added to the mixture of 2parts of sodium lauryl sulfate, 4 parts of sodium lignin sulfonate, 20parts of fine powders of water-containing synthetic silicon oxide and 54parts of clay. These ingredients were mixed while stirring by a juicemixer, thereby producing 20% wettable powders.

FORMULATION EXAMPLE 3 (GRANULE)

5 parts of each compound of the invention was mixed with 2 parts ofsodium dodecylbenzenesulfonate, 10 parts of bentonite and 83 parts ofclay, followed by thorough agitation. A suitable amount of water wasadded, and the mixture was further stirred. The mixture was granulatedby a granulator and air-dried, producing 5% granules.

FORMULATION EXAMPLE 4 (DUST)

1 part of each compound of the invention was dissolved in a suitableamount of acetone. To the solution were added 5 parts of fine powders ofwater-containing synthetic silicon oxide, 0.3 parts of acidic isopropylphosphate (PAP) and 93.7 parts of clay, followed by mixing and stirringby a juice mixer. Acetone was removed therefrom by evaporation,producing a 1% powder formulation.

FORMULATION EXAMPLE 5 (FLOWABLE PREPARATION)

20 parts of each compound of the invention was mixed with 20 parts ofwater containing 3 parts of polyoxyethylene tristyrylphenyl etherphosphoric acid ester triethanolamine and 0.2 parts of Rhodorsil 426R(manufactured by Rhodia Chimie). The mixture was pulverized by a mill(trade name: DYNO-Mill, manufactured by Willy A. Bachofen AG) using awet method, and further mixed with 60 parts of water containing 8 partsof propylene glycol and 0.32 parts of xanthane gum, thereby producing a20% suspension in water.

Test examples are given below to demonstrate that the compound of theinvention is useful as an active ingredient of a miticide.

TEST EXAMPLE 1 (MITICIDAL TEST ON TWO-SPOTTED SPIDER MITES)

A piece of non-woven fabric (4.5×5.5 cm) was suspended inside a plasticcup through an incision made in the lid of the plastic cup. After waterwas poured into the cup, the cup was covered with the lid. A kidney beanleaf (about 3.5×4.5 cm) was then placed on the sufficiently soaked,non-woven fabric. Another kidney bean leaf with two-spotted spider mites(about 30 mite samples) was placed on top of the first leaf, and thefabric and leaves were placed in a thermostatic chamber having atemperature of 25±2° C. and a humidity of 40%.

Miticidal formulations containing the compound of the invention (200ppm) were prepared by adding an aqueous solution (100 ppm) of Sorpol 355(manufactured by Toho Kagaku Co., Ltd.) to a methanol solution of thecompound of the invention.

These miticidal formulations were sprayed onto the leaves, and theleaves were air-dried and placed in a thermostatic chamber (25±2° C.,humidity 50%). The mortality rate of the two-spotted spider mites wascalculated after 2 days.

The compounds that exhibited the mortality rate of 50% or more are asfollows:

-   Compound Nos. 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16,    17, 18, 19, 20, 21, 22, 25, 30, 31, 32, 33, 35, 36, 38, 44, 45, 47,    48 and 49.

TEST EXAMPLE 2 (OVICIDAL TEST ON TWO-SPOTTED SPIDER MITES)

A piece of non-woven fabric (4.5×5.5 cm) was suspended inside a plasticcup through an incision made in the lid of the plastic cup. After waterwas poured into the cup, the cup was covered with the lid. A kidney beanleaf (about 3.5×4.5 cm) was then placed on the sufficiently soaked,non-woven fabric. Twenty female adults of two-spotted spider mite wereplaced on top of the leaf, and the fabric and leaf were placed in athermostatic chamber having a temperature of 25±2° C., a humidity of 40%and 16L8D.

The next day, after the number of the female adults was adjusted oncemore to 20, 2 ml of a miticidal formulation containing the compound ofthe invention (200 ppm) prepared in the same manner as in test example 1was sprayed onto the leaf, and the leaf was air-dried and placed in athermostatic chamber (25±2° C., humidity 50%). The ovicidal rate of thetwo-spotted spider mites was calculated 6 days after the spraying of themiticidal formulation.

The compounds that exhibited the mortality rate of 50% or more are asfollows:

-   Compound Nos. 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16,    17, 18, 19, 20, 21, 22, 25, 30, 31, 32, 33, 35, 36, 38, 44, 45, 48    and 49.

TEST EXAMPLE 3 (MITICIDAL TEST ON TWO-SPOTTED SPIDER MITES)

(1) As Test Compounds, The Following Compounds Were Used:

-   Test compound A: Compound No. 1 in table 3 (the compound of the    invention).-   Test compound B: Compound No. 2 in table 3 (the compound of the    invention).-   Test compound C: Compound No. 10 in table 3 (the compound of the    invention).-   Test compound D: Intermediate No. II-25 disclosed in table 2 on page    101 of Japanese Unexamined Patent Publication No. 158137/1999.    (2) Preparation of Emulsifiable Concentrate

Emulsifiable concentrates were prepared by adding the test compound,acetone and Sorpol 355 (surfactant) to distilled water. These emulsionswere set to contain acetone in the proportion of 5 wt. % and Sorpol 355in the proportion of 0.01 wt. %. The concentration of the test compoundwas set at 20 ppm.

(3) Miticidal Test

2 ml of each emulsifiable concentrate prepared above was sprayed onto apiece of a kidney bean leaf (2×4 cm) with 30 female adults oftwo-spotted spider mites. After being air-dried, the leaf was placed ina thermostatic chamber having a temperature of 25±1° C. The number oflive and dead mites was counted 2 days later. The mortality rate wascalculated using the following equation:Mortality rate={1−(survival rate in treated area)/(survival rate inuntreated area)}×100

The use of test compound A, B or C provided a mortality rate of 100%. Onthe other hand, the use of test compound D provided a mortality rate ofonly 10%.

The results clearly show that the compounds of the present inventionexhibit excellent mite control even when used at a low concentration.

TEST EXAMPLE 4 (MITICIDAL TEST ON TWO-SPOTTED SPIDER MITES)

(1) As Test Compounds, The Following Compounds Were Used:

-   Test compound A: Compound No. 1 in table 3 (the compound of the    invention).-   Test compound B: Compound No. 2 in table 3 (the compound of the    invention).-   Test compound C: Compound No. 10 in table 3 (the compound of the    invention).-   Test compound E: Compound No. a-683 disclosed in table 1-a on page    81 of Japanese Unexamined Patent Publication No. 158137/1999.    (2) Preparation of Emulsifiable Concentration

Emulsifiable concentrates were prepared by adding the test compound,acetone and Sorpol 355 (surfactant) to distilled water. These emulsionswere set to contain acetone in the proportion of 5 wt. % and Sorpol 355in the proportion of 0.01 wt. %. The concentration of the test compoundwas set at 200 ppm.

(3) Miticidal Test

30 ml of each emulsifiable concentrate prepared above was sprayed onto akidney bean plant (at the stage of true leaf growth) in a 9-cm pot, andair-dried. The pot was placed in a glass greenhouse. Each of the firstand second leaves was cut into a piece having a size of 3×5 cm, and 15female adults of two-spotted spider mite were introduced thereto after 3and 5 days of the spraying. Those pieces of leaves were placed in athermostatic chamber having a temperature of 25±1° C. The number of liveand dead mites was counted 2 days later. The mortality rate thereof wascalculated in the same manner as in test example 3 above. Table 5 showsthe result.

TABLE 5 Adjusted mortality rate (%) 3 days after spraying 5 days afterspraying Test compound A 100 95 Test compound B 100 93 Test compound C100 100 Test compound E 48 0

As shown in table 5, the compounds of the present invention exhibitexcellent mite control over a long period.

TEST EXAMPLE 5 (PHYTOTOXICITY TEST)

The 20% wettable powders obtained in formulation example 2 were dilutedto a predetermined degree and sprayed onto crops in a field in an amountof 0.4 liters/m². In a predetermined period after spraying, thedevelopment of phytotoxicity was observed by the naked eye. As testcompounds, test compounds A, B and C above were used. Table 6 shows theresult.

TABLE 6 Degree Phytotoxicity of Days after Test Test Test Crop (species)dilution spraying compound A compound B compound C Orange (sour orange)400 40 — None — Orange (mandarin) 1000 40 — None — Orange (iyo) 1000 40None None None Apple (fuji) 1000 27 None None None Apple (jonagold) 100014 None None None Tea (yabukita) 1000 21 None None None Pear (hosui)2000 21 None None None Grape (pione) 2000 28 None None None Eggplant(senryo) 1000 14 — None — Symbol “—”: no test conducted.

TEST EXAMPLE 6 (PHYTOTOXICITY TEST)

As test compounds, test compounds A, B and C above were used. The 20%wettable powders prepared in formulation example 2 were diluted 500 and1,000 times. These diluted wettable powders were sprayed onto riceplants, cucumbers, cabbages, spinaches, lettuces, tomatoes, leeks,carrots or kidney bean plants in an amount of 0.2 liters/m². Thedevelopment of phytotoxicity was examined by the naked eye 7 and 14 daysafter the spraying. As a result, no development of phytotoxicity wasobserved on the plants 7 and 14 days after the spraying of the wettablepowders.

Further, 20% wettable powders using test compound B were diluted 50, 100and 200 times, and sprayed onto cucumbers, cabbages, leeks or carrots inan amount of 0.2 liters/m². The development of phytotoxicity wasexamined by the naked eye 7 and 14 days after spraying. As a result, nodevelopment of phytotoxicity was observed on the plants 7 and 14 daysafter the spraying of the wettable powders.

1. An acylacetonitrile compound represented by the formula (1):

wherein R¹ represents —C(O)ZR²; R² represents C₁₋₆ alkyl, C₁₋₄haloalkyl, C₂₋₄ alkenyl, C₂₋₄ alkynyl, C₁₋₆ alkoxy-C₁₋₄ alkyl, C₁₋₄alkylthio-C₁₋₄ alkyl or benzyl; Z represents oxygen or sulfur; X and Yindependently represent halogen, C₁₋₆ alkyl or C₁₋₄ haloalkyl; m and nare independently an integer of 1 to 3; and m X's and n Y's may be thesame or different, respectively.
 2. An acylacetonitrile compoundaccording to claim 1, wherein Z in the formula (1) represents oxygen. 3.An acylacetonitrile compound according to claim 1, wherein X in theformula (1) represents halogen or C₁₋₆ alkyl.
 4. An acylacetonitrilecompound according to claim 1, wherein Y in the formula (1) representsat least one species selected from halogen and C₁₋₄ haloalkyl.
 5. Anacylacetonitrile compound according to claim 1, wherein Z representsoxygen, X represents C₁₋₆ alkyl, and Y represents C₁₋₄ haloalkyl in theformula (1).
 6. A process for preparing an acylacetonitrile compoundrepresented by the formula (1):

wherein R¹ represents —C(O)ZR²; R² represents C₁₋₆ alkyl, C₁₋₄haloalkyl, C₂₋₄ alkenyl, C₂₋₄ alkynyl, C₁₋₆ alkoxy-C₁₋₄ alkyl, C₁₋₄alkylthio-C₁₋₄ alkyl or benzyl; Z represents oxygen or sulfur; X and Yindependently represent halogen, C₁₋₆ alkyl or C₁₋₄ haloalkyl; m and nare independently an integer of 1 to 3; and m X's and n Y's may be thesame or different, respectively, the process comprising reacting anα-substituted-phenylacetonitrile compound represented by the formula(2):

wherein R¹, X and m are as defined above, with a benzoyl haliderepresented by the formula (3):

wherein Y and n are as defined above, and R³ represents halogen.
 7. Amiticide comprising as an active ingredient an acylacetonitrile compoundrepresented by the formula (1):

wherein R¹ represents —C(O)ZR²; R² represents C₁₋₆ alkyl, C₁₋₄haloalkyl, C₂₋₄ alkenyl, C₂₋₄ alkynyl, C₁₋₆ alkoxy-C₁₋₄ alkyl, C₁₋₄alkylthio-C₁₋₄ alkyl or benzyl; Z represents oxygen or sulfur; X and Yindependently represent halogen, C₁₋₆ alkyl or C₁₋₄ haloalkyl; m and nare independently an integer of 1 to 3; and m X's and n Y's may be thesame or different, respectively.
 8. A miticide according to claim 7,wherein Z in the formula (1) represents oxygen.
 9. A miticide accordingto claim 7, wherein X in the formula (1) represents halogen or C₁₋₆alkyl.
 10. A miticide according to claim 7, wherein Y in the formula (1)represents at least one species selected from halogen and C₁₋₄haloalkyl.
 11. A miticide according to claim 7, wherein Z representsoxygen, X represents C₁₋₆ alkyl, and Y represents C₁₋₄ haloalkyl in theformula (1).
 12. A miticide according to any of claim 7, which iseffective against plant-parasitic mites.
 13. A method for exterminatingmites comprising applying to the site an acylacetonitrile compoundrepresented by the formula (1):

wherein R¹ represents —C(O)ZR²; R² represents C₁₋₆ alkyl, C₁₋₄haloalkyl, C₂₋₄ alkenyl, C₂₋₄ alkynyl, C₁₋₆ alkoxy-C₁₋₄ alkyl, C₁₋₄alkylthio-C₁₋₄ alkyl or benzyl; Z represents oxygen or sulfur; X and Yindependently represent halogen, C₁₋₆ alkyl or C₁₋₄ haloalkyl; m and nare independently an integer of 1 to 3; and m X's and n Y's may be thesame or different, respectively.
 14. A method for producing a miticide,said method comprising producing said miticide by using onacylacetonitrile compound represented by the formula (1):

wherein R¹ represents —C(O)ZR²; R² represents C₁₋₆ alkyl, C₁₋₄haloalkyl, C₂₋₄ alkenyl, C₂₋₄ alkynyl, C₁₋₆ alkoxy-C₁₋₄ alkyl, C₁₋₄alkylthio-C₁₋₄ alkyl or benzyl; Z represents oxygen or sulfur; X and Yindependently represent halogen, C₁₋₆ alkyl or C₁₋₄ haloalkyl; m and nare independently an integer of 1 to 3; and m X's and n Y's may be thesame or different, respectively.
 15. An acylacetonitrile compoundaccording to claim 2, wherein X in the formula (1) represents halogen orC₁₋₆ alkyl.
 16. An acylacitonitrile compound according to claim 2,wherein Y in the formula (1) represents at least one species selectedform halogen and C₁₋₄ haloalkyl.
 17. A miticide according to claim 8,wherein X in the formula (1) represents halogen or C₁₋₆ alkyl.
 18. Amiticide according to calim 8, wherein Y in the formula (1) representsat least one species selected from halogen and C₁₋₄ haloalkyl. 19.Amiticide according to claim 11, which is effective againstplant-parasitic mites.